Grain oriented electrical steel sheet having improved glass film properties and low watt loss and process for producing same

ABSTRACT

The adhesiveness of a glass film and watt loss of a grain-oriented electrical steel sheet is improved by partially protruding the glass film into the steel sheet part thereof. To attain the partial protrusion, the steel sheet is subjected, prior or subsequent to decarburization annealing, to a treatment of the surface thereof to form unevennesses, by a mechanical device, e.g., brush rolling, buff polishing, marking-off, sand papering, and grinding.

This application is a continuation of application Ser. No. 07/089,685filed Aug. 26, 1987, abandoned, which is a division of Ser. No.06/938,648 filed Dec. 15, 1986 now U.S. Pat. No. 4,897,131.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a grain-oriented electrical steel sheethaving improved glass film properties and a low watt loss, and a processfor producing the same.

2. Description of the Related Arts

Grain-oriented electrical steel sheet is mainly used for the cores ofelectrical appliances, such as transformers and power generators. Forsuch usage, it is important that the grain-oriented electrical steelsheet have excellent magnetic properties such as the watt-losscharacteristics and excitation characteristics, and excellent glass filmproperties. Usually, the grain-oriented electrical steel sheet isproduced by the steps of hot-rolling a silicon-steel slab containing 4%or less of silicon, and if necessary, hot-coil annealing; cold-rollingonce or twice or more with an intermediate annealing therebetween toobtain a cold-rolled sheet having a final sheet thickness;decarburization-annealing; applying an annealing separator mainlycomposed of MgO; finishing annealing to develop secondary recrystallizedgrains having a Goss texture; removing impurities such as S and N;forming a glass film; and finally, heat-flattening and treating with aninsulating coating.

An improvement of the magnetic properties, particularly the watt loss,together with an improvement of the glass film has been investigated,and it is known, as shown in J. Appl. Phys. 38, (1967), pp 1104 ˜1108,that a reduction in the sheet thickness and grain-refinement of agrain-oriented electrical steel sheet effectively reduces the watt loss.Reducing the sheet gauge is an effective method of reducing the wattloss, but the watt loss is increased due to an increase in the eddycurrent loss when the sheet thickness becomes less than a predeterminedthickness. An improvement of the watt loss by grain-refinement isinherently limited by the secondary recrystallization phenomenon, whichis utilized to attain a growth of grains having the Goss texture andenhance the orientation degree.

For an improvement of a glass film, Japanese Unexamined PatentPublication (Kokai) No. 50-71526, for example, describes the pickling ofa grain-oriented electrical steel sheet, which was cold-rolled to afinal thickness, in such a manner that 3 g/m² or more of its surfacelayer is uniformly removed, thereby removing the surface deposits and asuperficial part of the steel part thereof, and thus enabling a uniformprogression in the decarburization reaction and the oxide-formationreaction This, in turn, leads to a formation of an MgO-SiO₂ seriesinsulating film having an improved uniformity and adhesiveness after thedecarburization annealing, application of an annealing separator, andfinishing annealing.

Japanese Unexamined Patent Publication (Kokai) No. 57-101673 disclosesthat, after the decarburization annealing of a grain-oriented electricalsteel strip cold-rolled to a final thickness and before the applicationof the annealing separator, such as MgO and the like, the surface of thesteel strip is subjected to grinding or pickling so as to remove 0.025to 0.5 g/m² of the surface per one side, thereby removing the oxide filmconstituting the surface layer of a grain-oriented electrical steelsheet. Subsequently, the annealing separator is applied, and finishingannealing is carried out. The thus-formed glass film has a uniform, greyappearance, and an improved adhesiveness.

Japanese Unexamined Patent Publication (Kokai) No. 61-96082 proposes togrind and clean the surface of a steel sheet, without formingunevennesses, by a grinding means consisting of soft materials includinga carborundum abrasive and an alundum abrasive, thereby enabling auniform subscale of SiO₂ to be formed during the decarburizationannealing and a uniform and dense film to be formed during the finishingannealing.

SUMMARY OF THE INVENTION

The prior methods attained improvements in the glass film properties,such as adhesiveness, and in the magnetic properties, but are notsatisfactory.

When improvements in the glass film properties are attempted bythickening the film, this can be effectively attained by thickening theoxide layer consisting mainly of SiO₂ in the decarburization annealing.In this case, measures such as enhancing the P H₂ O/P H₂ and elongatingthe soaking time become necessary. These measures inevitably lead to anincrease in the amount of Fe series oxide formed, such as fayallite (Fe₂SiO₄), FeO, and the like, and thus to a degradation of the qualities ofa glass film and an adverse influence on the inhibitors. Particularly,the high Si materials for improving the magnetic properties, especiallyreducing the watt loss, and materials with a special additive-composingelement or compound as inhibitors, are concentrated in the surface layeror are selectively oxidized, with the result that a decarburizationfailure may occur or the formation of a decarburization-oxidized filmmay be impaired.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a grain-orientedelectrical steel sheet having improved glass film properties and a lowwatt loss, and a process for producing the same.

Another object of the present invention is to provide a method forproducing a grain-oriented electrical steel sheet having improved glassfilm properties and a low watt loss, and a process for producing thesame.

A further object of the present invention is to provide a method forproducing a grain-oriented electrical steel sheet, which method enablesan improvement in the glass film properties and a reduction of the wattloss of high Si materials and materials with special additives, thesematerials being difficult to produce with a high productivity by theprior art methods.

The present inventors discovered that, when an oxide is formed in such away that it partially protrudes into the steel sheet part or side of agrain-oriented electrical steel sheet, an anchoring effect is generated,thereby dramatically improving the adhesiveness of a glass film andgreatly enhancing the tension effect of a film. The discoveries made bythe present inventors are hereinafter described in detail.

The present inventors carried out investigations into the influence ofthe shapes of the oxide layer formed on the steel sheet during thedecarburization annealing, and of the glass film formed due to thereactions between the oxide layer and annealing separator, upon theadhesiveness of a glass film, tension at the steel sheet, and the wattloss. The layer, which is constituted at the steel sheet part or side byan oxide(s) of either SiO₂ -enriched Fe oxide, an ordinary oxide, or anoxide partially containing forsterite, is hereinafter referred to as theinner oxide layer.

In accordance with the present invention, there is provided agrain-oriented electrical steel sheet having a glass film on the steelpart thereof, characterized by forming an oxide partially protrudinginto the steel 5 part, thereby improving the adhesiveness of the glassfilm and the watt loss.

There is also provided a method for producing a grain-orientedelectrical steel sheet having improved glass film adhesiveness and animproved watt loss, comprising the steps of hot-rolling a silicon-steelslab; annealing; cold-rolling once or twice or more with an intermediateannealing therebetween; decarburization-annealing; applying an annealingseparator; and finishing annealing in which a glass film is formed onthe silicon steel sheet, characterized by subjecting the steel sheet,prior or subsequent to the decarburization annealing, to a treatment ofthe surface thereof so as to form unevennesses, concave parts of whichprovide sites at which oxide is protruded into the silicon steel partduring the finishing annealing or during the decarburization annealingand the finishing annealing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1(A) and (B) are metal-microscope photographs of the inner oxidelayers formed by the method of the present invention and by thecomparative method, respectively;

FIG. 2 illustrates the influence exerted by depth of the protrusion ofthe inner oxide layer upon the adhesiveness of a glass film;

FIG. 3 illustrates the influence exerted by the depth of protrusion ofthe inner oxide layer upon the tension of the steel sheet;

FIG. 4 illustrates the influence exerted by the depth of protrusion ofthe inner oxide layer upon the watt loss;

FIG. 5 illustrates the influence of the distance between theunevennesses formed on a steel sheet upon the watt loss;

FIGS. 6(A) and (B) are similar photographs to those shown in FIGS. 1(A)and 1(B), respectively, with regard to the effect of activation bypolishing and light pickling;

FIG. 7 is a drawing of curves of the potential of oxide films in adilute sulfuric acid;

FIG. 8 illustrates the influence of polishing the roughness of a steelsheet surface and decarburization annealing-conditions upon theadhesiveness of a glass film;

FIG. 9 illustrates the influence of polishing the roughness of a steelsheet surface and decarburization annealing-conditions upon the tensionof a glass film.

FIG. 10 illustrates the influence of polishing the roughness of a steelsheet surface and decarburization annealing-conditions upon the wattloss.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In an experiment by the present inventors, the surfaces of cold-rolledsteel sheets of grain-oriented electrical steel, which were cold-rolledto a thickness of 0.225 mm, were polished by sheets of sandpaper havingdifferent grades to form sharp and minute unevennesses, and thendecarburization annealed to form the depth and shapes of the inner oxidelayer. Subsequently, an annealing separator mainly composed of MgO wasapplied and finishing annealing was carried out. The inner oxide layerwas, as shown in FIG. 1(B), virtually uniformly thick on steel which hadnot been polished. Conversely, on steel which had been polished, partsof the inner oxide layer were thicker than the average thickness, andwere thick enough to protrude into the steel sheet side. Theadhesiveness of the glass film was tested, after the application of theannealing separator and then finishing annealing, by bending to around10 mmφ, i.e., more severe than the usual condition of bending to around20˜50 mmφ, to investigate the peel area percentage of the glass film.The results are shown in FIG. 2. In the samples A and B, in which theformed inner oxide layer partially protrudes into the steel sheet side,no peeling occurs and the adhesiveness is extremely good. In addition,the tension imparted to the steel sheet is greatly increased, as shownin FIG. 3. FIG. 4 shows that the watt loss is greatly decreased toattain a low watt loss.

When a deep inner oxide layer was formed, the glass film formed by thefinishing annealing was also deep. The unevennesses do not lead torefinement of secondary recrystallized grains at parts of agrain-oriented electrical steel sheet where the unevennesses are formed.

The present invention was completed based on the discoveries asdescribed above and in more detail hereafter.

In the present invention, preferably the inner oxide layer partiallyprotrudes into the steel sheet side of a grain-oriented electrical steelsheet by a depth of approximately 2 to 15 μm , exceeding the averagethickness thereof. The term "partially" herein indicates a continuous ordiscontinuous state of an inner oxide layer having protruding parts atan equal-distance or non-equi distance.

Preferably, the above mentioned surface treatment is carried out priorto the decarburization-annealing, by an optical means, particularlyirradiation of laser, e.g., YAG or CO₂ laser, and/or a mechanical means,particularly brush rolling, buff polishing, marking-off, sand papering,and grinding, and further, sharp and minute unevennesses are formed bythe mechanical and/or optical means on the entire surface of the steelsheet within +30 degrees to the direction perpendicular to the rollingdirection, and at a distance of less than 1 mm. The surface treatment iscarried out on either or both of the surfaces of the sheet to form theunevennesses on at least 35%, preferably 50%, by area of the steelsheet. The surface of the steel sheet is activated due to this formationof unevennesses, and a thick oxide is formed during the decarburizationannealing and finishing annealing and protrudes into the steel sheet viathe activated parts.

The SiO₂ is enriched in the oxide formed during the decarburizationannealing and finishing annealing due to the activating, with the resultthat the glass film properties are improved, and further, the steelsheet is shielded from the atmosphere during the finishing annealing,thereby suppressing reaction between the inhibitors, such as MnS andAlN, and the annealing atmosphere, and stably maintaining them to a hightemperature. Therefore, a stable secondary recrystallization takesplace.

The SiO₂ enriched layer tends to impede decarburization and may lead toa degradation of the watt loss. Therefore, it is necessary to provideannealing conditions more favorable than those of the conventionalmethod without the activation. The annealing conditions are atemperature of 800˜860° C., on atmosphere of N₂, H₂ , or a mixture of N₂+H₂ , and a P H₂ O/P H₂ ≧0.40.

When sharp and minute unevennesses are formed, the surface layer of thesteel sheet is removed by an amount of generally 2.0 g/m² or more, whichis greater than the amount of from 0.025 to 0.5 g/m² incurred whenremoving the oxide film on the surface of a steel sheet as described inJapanese Unexamined Patent Publication (Kokai) No. 57-101673. Therefore,the yield is a little decreased in the present invention, but this isnegligible in the light of the dramatic improvement in the glass filmproperties and watt loss characteristics.

A further reduction of the watt loss is attained by setting the distancebetween adjacent sharp and minute unevennesses to an extremely narrowdistance of less than 1 mm, and orienting them to within +30 degreesrelative to the direction perpendicular to the rolling direction. Theunevennesses should be formed before the completion of thedecarburization annealing, preferably before starting thedecarburization annealing or during the temperature-elevation period inthe decarburization annealing process.

Note, it is known to form minute marks, such as linear flaws, on a9rain-oriented electrical steel sheet with a space between the marks, soas to subdivide the magnetic domains. The formation distance of themarks is allegedly more than 1 mm, but in practice, is from 3 to 12 mm.Allegedly, the watt loss increases at a minute mark distance of lessthan 1 mm when subdividing the magnetic domains, contrary to the case ofthe present invention.

FIG. 5 shows that sharp and minute unevennesses formed at a distance ofless than 1 mm, preferably less than 0.5 mm, are advantageous forreducing the watt loss. The adhesivity of a glass film is also enhancedwhen the distance between the unevennesses is less than 1 mm. Thedistance is between the adjacent convex parts of the unevennesses.

In an experiment by the present inventors, cold-rolled steel sheets of agrain-oriented electrical steel sheet, which were cold-rolled to a finalthickness of 0.30 mm, were polished by a brush roll having abrasivegrains embedded therein. The average roughness Ra and maximum roughnessR_(T) were 0.5 μm and 4.5 μm , respectively. Subsequently, lightpickling by a dilute sulfuric acid was carried out to attain a weightloss of approximately 2.5 g/m² or more, and activate the surfaces of thesteel sheets. These steel sheets were decarburization annealed at 850°C. in an N₂ +H₂ wet atmosphere having a P H₂ O/P H₂ of 0.4. Theannealing separator mainly composed of MgO was then applied andfinishing annealing at 1200° C. for 20 hours carried out. FIG. 6(A)shows the inner oxide layer of the comparative sample, which has notbeen polished and lightly pickled. The inner oxide layer of thecomparative sample is virtually uniformly thick. The inner oxide layerof the sample shown in FIG. 6(B) has a thickness such that parts thereofare thicker than the average thickness and protrude into the steel sheetpart. FIG. 7 shows the solution curves (potential curve) of oxide filmson the decarburization annealed sheets in dilute sulfuric acid. As shownin FIG. 7 for the material B treated by polishing and then lightpickling (activated), the potential peak corresponding to the SiO₂ layeris high, which indicates that a thick SiO₂ layer has been formed.

Table 1 shows the magnetic properties of grain-oriented electrical steelsheets treated by the different processes.

                  TABLE 1                                                         ______________________________________                                                      Magnetic                                                                      Properties  Tension of                                                Treating      B.sub.10                                                                              W.sub.17/50                                                                           Glass Film                                No.   Conditions    (T)     (W/kg)  (kg/mm.sup.2)                             ______________________________________                                        1     Brush         1.940   0.96    0.58                                            Polishing                                                               2     Brush Polishing +                                                                           1.937   0.94    0.62                                            Light Pickling                                                          3     Comparative   1.946   1.02    0.30                                            Material                                                                      (without                                                                      treatment)                                                              ______________________________________                                    

The amount removed by light pickling is preferably 2.5 g/m² or less.When the amount removed exceeds 2.5 g/m², the pickling is so severe thatthe surface of the steel sheet is roughened, and further, the sharp andminute unevenness formed by a mechanical means or the like are deformed.In this case, the unevennesses do not have the function of forming sharpoxide protrusions.

The depth of the unevennesses is preferably from 0.3 to 5 μm , in termsof the average roughness Ra, and approximately 15 μm in terms of themaximum roughness R_(T).

Prior or subsequent to the decarburization annealing, preferably strainis imparted to a steel sheet by laser irradiation, marking off, a knife,or a tooth form roll. The distance between the strained regions ispreferably from approximately 1 to 20 mm, and the angle of the strainedregions relative to the rolling direction is preferably from 30 to 90degrees. The strain, in combination with the activation of the surfaceof the steel sheet due to sharp and minute strains, contributes to afurther reduction of the watt loss.

The direction of, for example, polishing for forming the sharp andminute unevenness, is not limited in any way.

The processes for producing the grain-oriented electrical steel sheetaccording to the present invention are described hereinafter.

The steel composition of a grain-oriented electrical steel sheet andproduction conditions until cold-rolling need not be specified sincethey are well known. The steels used may contain from 0.04 to 0.10% of Cand from 2.0 to 4.0% of Si. Any adequate inhibitors, such as AlN, MnS,MnSe, BN, Cu₂ S, and the like, may be used. If necessary, elements suchas Cu, Sn, Cr, Ni, Mo, Sn, and the like may be added.

Note, conventional industrially produced grain-oriented electrical steelsheets had a thickness of 0.30 mm, but 0.23 mm, 0.20 mm, 0.175 mm, and0.150 mm thick grain-oriented electrical steel sheets have beendeveloped and are now produced, to reduce the eddy current loss. One ofthe greatest hindrances to the production of thin grain-orientedelectrical steel sheets is the instability of the secondaryrecrystallization. Japanese Unexamined Patent Publication (Kokai) No.58-217630 proposed the addition of Sn and Cu for stabilizing thesecondary recrystallization, and Japanese Unexamined Patent Publicationproposed predecarburization annealing. In the present invention,however, the secondary recrystallization of 0.23 mm or less thingrain-oriented electrical steel sheets is advantageously stabilized.

After the cold-rolling for obtaining the final thickness,decarburization annealing is carried out.

Preferably, the decarburization annealing promotes the decarburizationand oxidation reaction. This is attained by enhancing the dew point, forexample, from 60 to 70° C., in the presence of a 25% N₂ +75% H₂atmosphere at 850° C.

In an experiment by the present inventors, the surfaces of cold-rolledsheets of a grain-oriented electrical steel, which were cold-rolled to afinal thickness of 0.225 mm, were polished by sheets of sand paperhaving different grades to form sharp and minute unevennesses.Subsequently, decarburization annealing was carried out at 850° C. in anN₂ +H₂ atmosphere while varying the P H₂ O/P H₂ ratio to 0.30, 0.40, and0.50. Subsequently, an annealing separator composed mainly of MgO wasapplied and the finishing annealing was then carried out.

Referring to FIG. 8, oxide peeling does not occur in the samples whichare decarburization-annealed at a P H₂ O/P H₂ =0.40 and 0.50. Polishinghas a tendency to considerably enhance the tension of a film, as shownin FIG. 9, and the watt loss is improved considerably at a P H₂ O/P H₂=0.40, but is degraded when compared with the an unpolished sample at aP H₂ O/P H₂ <0.40, as shown in FIG. 10.

After the decarburization annealing, an annealing separator, which ismainly composed of MgO and in which additives, TiO₂ , B compounds, suchas H₃ BO₃, Na₂ B₄ O₇, and the like, SrS, SnS, CuS, and the like areadded, is applied and dried.

The finishing annealing is then carried out, and the oxide, having athickness exceeding the average thickness and partially protruding intothe steel sheet side, and the annealing separator are caused to reactwith each other, and thus a glass film is formed. The glass film iscontiguous to the oxide which partially deeply protrudes into the steelsheet side. Alternatively, the glass film per se deeply protrudes intothe steel sheet side. Therefore, the adhesiveness of the glass film isconsiderably enhanced, and furthermore, the tension which the glass filmimparts to the steel sheet is drastically enhanced, to obtain steelsheets having an extremely low watt loss. The secondaryrecrystallization is satisfactory even in thin material, for example,0.15 mm thick material, because the decomposition and disappearance ofthe inhibitors is suppressed due to the shielding effect of the oxideformed in the decarburization annealing.

Subsequently, a flattening annealing is carried out, and then aninsulating coating solution, which contains one or more of phosphoricacid, phosphates, such as aluminum phosphate, magnesium phosphate, zincphosphate, and calcium phosphate, chromic acid, chromates, such asmagnesium chromate and the like, bichromates, and colloidal silica, isapplied on the steel sheet, followed by baking at a temperature of 350°C. or more to form an insulating film. The advantages of the presentinvention will be further clarified by the following examples, which inno way limit the present invention.

EXAMPLE 1

A silicon steel-slab containing 0.060% of C, 2.95% of Si, 0.070% of Mn,0.029% of Al, 0.025% of S, and a balance of iron was subjected, by aknown method, to hot-rolling, annealing, and cold-rolling to obtain 0.27mm thick sheets. On the sheets, sharp and minute unevennesses wereformed in a direction perpendicular to the rolling direction, with adistance of 0.8 mm or less and 5 mm and an average roughness of 0.5 μmand 2.0 μm , by brush rolling and buff polishing.

Then, decarburization annealing was carried out at 850° C. for 120seconds in an N+H₂ humid atmosphere (P H₂ O/P H₂ =0.40). Subsequently,the application of an annealing separator, and a finishing annealing at1200° C. for 20 hours, were carried out. The glass film properties andthe magnetic properties in this state were as shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Treatment    Magnetic    Glass Film                                           Conditions   Properties  10 mmφ                                                                              Tension of                                        Average   (T)    (W/kg) Adhesivity                                                                            Glass Film                             Method Roughness B.sub.10                                                                             W.sub.17/50                                                                          (Bending)                                                                             (kg/mm.sup.2)                          ______________________________________                                        Brush  0.5 μm 1.929  0.94   Slight peel                                                                           0.48                                   Rolls  2.0 μm 1.922  0.92   No peel 0.60                                                                  at all                                         Buff   0.5 μm 1.925  0.92   Slight peel                                                                           0.45                                   Polishing                                                                            2.0 μm 1.920  0.93   No peel 0.62                                                                  at all                                         Comparative  1.938  0.98     Peel on 0.28                                     Material 1                   entire                                           (Without Polishing)          surface                                          Comparative  1.937  0.97     Peel on 0.26                                     Material 2                   entire                                           (Distance between            surface                                          Convex and Concave                                                            -5 mm)                                                                        ______________________________________                                    

As is apparent from Table 2, according to the present invention,grain-oriented electrical steel sheets having a high film tension, animproved adhesiveness, and a low watt loss were obtained.

EXAMPLE 2

A silicon steel-slab containing 0.070% of C, 3.23% of Si, 0.075% of Mn,0.025% of Al, 0.026% of S, and balance of iron was subjected, by a knownmethod, to hot-rolling, annealing, and cold-rolling to obtain 0.30 mmthick sheets. The surface of the cold-rolled sheets was polished by abrush-roll with an embedded polishing grindstones to obtain an averagesurface roughness of 1.0 μm . Several of the sheets were furthersubjected, after the polishing treatment, to a light pickling treatmentby 5% sulfuric acid, while varying the weight loss due to pickling.

Then, decarburization annealing was carried out at 850° C. in an N₂ +H₂humid atmosphere (P H₂ O/P H₂ =0.38), and subsequently, the applicationof an annealing separator, and a finishing annealing at 1200° C. for 20hours, were carried out. The glass film properties and magneticproperties in this state were as shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Treatment Conditions                                                                       Magnetic                                                                             Glass Film                                                Polishing                                                                          Weight Loss by                                                                        Properties    Tension of                                         depth                                                                              Pickling (g/m.sup.2)                                                                  W.sub.17/50                                                                       B.sub.10                                                                         Appearance                                                                           Glass Film                                                                           Adhesivity                                  __________________________________________________________________________    μm                                                                              --      0.930                                                                             1.928                                                                            Slight Non-                                                                          0.25 kg/mm.sup.2                                                                     Δ                                                         uniformity                                                1.0  none    0.885                                                                             1.935                                                                            Uniform and                                                                          0.46   ⊚                                                Excellent                                                 1.0  none    0.850                                                                             1.933                                                                            Uniform and                                                                          0.58   ⊚                                                Excellent                                                 1.0  none    0.852                                                                             1.925                                                                            Uniform and                                                                          0.60   ⊚                                                Excellent                                                 1.0  0.5     0.870                                                                             1.943                                                                            Uniform and                                                                          0.50   ⊚                                                Excellent                                                 1.0  1.0     0.836                                                                             1.937                                                                            Uniform and                                                                          0.62   ⊚                                                Excellent                                                 1.0  2.0     0.835                                                                             1.930                                                                            Uniform and                                                                          0.62   ⊚                                                Excellent                                                 __________________________________________________________________________     Remarks: Adhesivity  Bending around 10 mmφ after coating an insulatin     coating                                                                  

As is apparent from Table 3, according to the present invention,grain-oriented electrical steel sheets having a high film tension, animproved adhesiveness, and a low watt loss are obtained.

EXAMPLE 3

A silicon steel-slab containing 0.065% of C, 3.25% of Si, 0.068% of Mn,0.027% of Al, 0.023% of S, 0.07% of Cu, 0.12% of Sn, and a balance ofiron was subjected, by a known method, to hot-rolling, annealing, andcold-rolling to obtain 0.225 mm thick sheets. Note, sheets which werenot further subjected to a polishing-treatment are designated as"without treatment". An area of 50% of the steel sheets was polished bysand paper, while varying the grade thereof, to form unevennesses interms of 12 μm, 9 μm, 7 μm, 5 μm, and 3 μm of the surface roughness ofthe steel sheet.

Then, the processes of decarburization annealing, application of anannealing separator, and finishing annealing were carried out, andsubsequently, product sheets were obtained by heat-flattening after theapplication of an insulating coating. The properties of the films andthe magnetic properties of the product sheets were then measured and theresults were as shown in Table 3. Note, an investigation of theadhesiveness of the films under an ordinary condition of bending toaround 20˜50 mmφ revealed that no peeling occurred even for materialsthat were "without treatment". Accordingly, a more severe bending to 10mmφ was carried out.

                  TABLE 4                                                         ______________________________________                                                       Magnetic                                                                      Properties  Adhesivity                                         Surface          W.sub.17/50                                                                             B.sub.10                                                                              of Film                                    Roughness (μm)                                                                              (W/kg)    (T)     (%)                                        ______________________________________                                        1    3               0.87      1.94  20                                       2    5               0.80      1.94  3                                        3    7               0.79      1.93  0                                        4    9               0.83      1.92  0                                        5    12              0.88      1.92  0                                        6    Comparative Material                                                                          0.91      1.93  75                                            (without treatment)                                                      ______________________________________                                         Remarks: Area percentage of a film peeled by bending around 10 mmφ.  

EXAMPLE 4

A silicon steel-slab containing 0.060% of C, 3.15% of Si, 0.070% of Mn,0.030% of Al, 0.024% of S, 0.07% of Cu, 0.13% of Sn, and a balance ofiron was subjected, by a known method, to hot-rolling, annealing, andcold-rolling to obtain 0.29 mm thick sheets. An area of 80% of the steelsheets was treated by square shot-blasting to form unevennesses from 25to 10 μm in depth.

Then, the processes of decarburization annealing, application of anannealing separator, and finishing annealing were carried out, andsubsequently, the product sheets were obtained by heat-flattening afterthe application of an insulating coating. The properties of the filmsand the magnetic properties of the product sheets were measured, and theresults were as shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                         Magnetic                                                     Indentation      Properties    Adhesivity                                     by Shot          W.sub.17/50                                                                             B.sub.10                                                                              of Film                                    Treatment (μm)                                                                              (W/kg)    (T)     (%)                                        ______________________________________                                        1    2.5             0.97      1.94  20                                       2    5               0.95      1.95  5                                        3    7.5             0.94      1.94  0                                        4    10              0.97      1.93  0                                        5    Comparative Material                                                                          1.04      1.94  70                                            (without treatment)                                                      ______________________________________                                         Remarks: Area percentage of a film peeled by bending around 10 mmφ.  

EXAMPLE 5

A silicon steel-slab containing 0.058% of C, 3.10% of Si, 0.065% of Mn,0.0010% of Al, 0.024% of S, and balance of iron was subjected to a wellknown double rolling method to obtain 0.265 mm thick steel sheets.Samples of these sheets were designated as "without treatment". An areaof approximately 70% of the steel sheets was polished by a brush roll,to form unevennesses in terns of 3˜4 μm, 8˜10 μm, and 12˜15 μm of thesurface roughness of the steel sheet. Then, the processes ofdecarburization annealing, application of an annealing separator, andfinishing annealing were carried out, and subsequently, the productsheets were obtained by heat-flattening after the application of aninsulating coating. The properties of the films and the magneticproperties of the product sheets were measured, and the results were asshown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Brush Roll                                                                    Treatment    Magnetic                                                         Conditions   Properties  Adhesivity                                                                              Tension of                                 (Treatment   W.sub.17/50                                                                            B.sub.10                                                                             of Film Glass film                               Depth: μm)                                                                              (W/kg)   (T)    (%)     (kg/cm.sup.2)                            ______________________________________                                        1   3˜4    1.10     1.87 10      0.48                                   2   5˜6    1.12     1.86 0       0.52                                   3    8˜10  1.15     1.85 0       0.60                                   4   12˜15  1.18     1.85 0       0.65                                   5   Comparative  1.20     1.86 60      0.35                                       Material                                                                      (without                                                                      treatment)                                                                ______________________________________                                         Remarks: Area percentage of a film peeled by bending around 10 mmφ.  

EXAMPLE 6

The 0.225 mm thick cold-rolled steel sheets prepared in the same manneras in Example 3 were decarburization-annealed at 850° C. for 3 minutesin an N₂ +H₂ humid atmosphere. An area of approximately 50% of thedecarburization-annealed steel sheets was polished, by a brush roll, toform unevennesses in terms of 12 ˜15 μm, 8˜10 μm, 4˜6 μm, and 2˜3 μm ofthe surface roughness of the steel sheet.

Subsequently, with regard to the samples that weredecarburization-annealed alone and the samples decarburization-annealedand then polished, the application of an annealing separator and thenfinishing annealing at 1200° C. for 20 hours were carried out andsubsequently, the product sheets were obtained by heat-flattening afterthe application of an insulating coating. The properties of the filmsand the magnetic properties of the product sheets were measured, and theresults were as shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                            Magnetic                                                                      Properties                                                       Surface Roughness  W.sub.17/50                                                                            B.sub.10                                   No.    (μm)            (W/kg)   (T)                                        ______________________________________                                        1      2˜3          0.84     1.95                                       2      4˜6          0.77     1.93                                       3       8˜10        0.79     1.92                                       4      12˜15        0.83     1.92                                       5      Comparative Material                                                                             0.92     1.95                                              (without treatment)                                                    ______________________________________                                    

EXAMPLE 7

A silicon steel-slab containing 0.080% of C, 3.20% of Si, 0.065% of Mn,0.035% of Al, 0.024% of S, 0.060% of Cu, 0.11% of Sn, and a balance ofiron was subjected, by a known method, to hot-rolling, annealing, andcold-rolling to obtain 0.225 mm thick sheets. Sheets which were notpolished are designated as "without treatment". The steel sheets werepolished, while varying the area percentage of the parts polished to20%, 50%, 70%, and 95%, by sand paper, to form unevennesses in terms of5 μm of the surface roughness of the steel sheet. The steel sheets werethen decarburization-annealed in an N₂ +H₂ humid atmosphere, andsubsequently, the application of an annealing separator, in which 6.5parts by weight of TiO₂ was blended with respect to 100 parts by weightof MgO, and then finishing annealing at 1200° C. for 20 hours, werecarried out.

The properties of the films and the magnetic properties were thenmeasured, and the results were as shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________                                         Magnetic                                              Properties of Glass Film                                                                              Properties                                  Area Percentage of                                                                              Tension                                                                             Adhesivity                                                                              W.sub.17/50                                                                        B.sub.10                            No.                                                                              Polished Parts (%)                                                                      Appearance                                                                            (kg/mm.sup.2)                                                                       (10 mmφ Bending)                                                                    (W/kg)                                                                             (T)                                 __________________________________________________________________________    1  20        Slightly thin,                                                                        0.26  Δ   0.95 1.93                                             Nonuniformity                                                                 like Gas Marks                                                   2  50        Uniform, thick                                                                        0.48  ⊚                                                                        0.88 1.92                                             and excellent                                                    3  70        Uniform, thick                                                                        0.55  ⊚                                                                        0.85 1.92                                             and excellent                                                    4  95        Uniform, thick                                                                        0.58  ⊚                                                                        0.85 1.91                                             and excellent                                                    5   0        Slightly thin,                                                                        0.25  X         0.97 1.94                                   (Comparative                                                                            Nonuniformity                                                       Material) like Gas Marks                                                   __________________________________________________________________________     Remarks: Criterion of Adhesivity                                              ⊚: No peeling                                                  Δ: Peeling occurrence at area of 20˜50%                           X: Peeling occurrence at area of 50% or more                             

EXAMPLE 8

Cold-rolled steel sheets 0.18 mm thick were prepared anddecarburization-annealed in the same manner as in Example 7. Thedecarburization-annealed steel sheets were then polished, while varyingthe area percentage of the polished parts to 15%, 50%, 80%, and 95%, bya brush roll, to form polished parts 3 μm in depth Subsequently, theapplication of an annealing separator, in which 6.5 parts by weight ofTiO was blended with respect to 100 parts by weight of MgO, and thenfinishing annealing at 1200° C. for 20 hours, were carried out. Theproperties of the films and the magnetic properties were then measured,and the results were as shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________                                         Magnetic                                              Properties of Glass Film                                                                              Properties                                  Area Percentage of                                                                              Tension                                                                             Adhesivity                                                                              W.sub.17/50                                                                        B.sub.10                            No.                                                                              Polished Parts (%)                                                                      Appearance                                                                            (kg/mm.sup.2)                                                                       (10 mmφ Bending)                                                                    (W/kg)                                                                             (T)                                 __________________________________________________________________________    1  15        Slightly thin,                                                                        0.30  Δ   0.92 1.93                                             Nonuniformity                                                                 like Gas Marks                                                   2  50        Uniform and                                                                           0.42  ⊚                                                                        0.82 1.93                                             excellent                                                        3  80        Uniform and                                                                           0.48  ⊚                                                                        0.82 1.92                                             excellent                                                        4  95        Uniform and                                                                           0.48  ⊚                                                                        0.80 1.90                                             excellent                                                        5   0        Slightly thin,                                                                        0.28  X         0.93 1.93                                   (Comparative                                                                            Nonuniformity                                                       Material) like Gas Marks                                                   __________________________________________________________________________

EXAMPLE 9

A silicon steel-slab containing 0.078% of C, 3.28% of Si, 0.065% of Mn,0.033% of Al, 0.023% of S, 0.070% of Cu, 0.10% of Sn, and a balance ofiron was subjected, by a known method, to hot-rolling, annealing, andcold-rolling to obtain 0.30 mm thick sheets. Sheets which were notpolished are designated as "without treatment". Two surface activationtreatments were carried out, as follows: samples of the steel sheetswere polished, while varying the area percentage of the polished partsto 50%, and 85%, by sand paper, to form polished parts 3 μm inroughness, and in addition to these samples, polished and marked-offsamples were prepared by treatment by a knife edge to introduce 10 μmdeep strains at a distance of 5 mm and in a direction perpendicular tothe rolling direction. The steel sheets were thendecarburization-annealed in a humid atmosphere, and subsequently, theapplication of an annealing separator, and then finishing annealing at1200° C. for 20 hours, were carried out.

The properties of the films and the magnetic properties were thenmeasured, and the results were as shown in Table 10.

                                      TABLE 10                                    __________________________________________________________________________                                           Magnetic                               Conditions for Properties of Glass Film                                                                              Properties                             Surface Activation     Adhesivity                                                                              Tension                                                                             B.sub.10                                                                         W.sub.17/50                         No.                                                                              Polishing                                                                          Marking Off                                                                          Appearance                                                                            (10 mmφ Bending)                                                                    (kg/mm.sup.2)                                                                       (T)                                                                              (W/kg)                              __________________________________________________________________________    1  3μ                                                                              No     Thick, uniform,                                                                       ⊚                                                                        0.53  1.93                                                                             0.98                                   50%         excellent                                                      2  3μ                                                                              Yes    Thick, uniform,                                                                       ⊚                                                                        0.52  1.93                                                                             0.95                                   50%         excellent                                                      3  3μ                                                                              No     Thick, uniform,                                                                       ⊚                                                                        0.56  1.92                                                                             0.99                                   85%         excellent                                                      4  3μ                                                                              Yes    Thick, uniform,                                                                       ⊚                                                                        0.56  1.92                                                                             0.92                                   85%         excellent                                                      5  No   No     Slightly thin,                                                                        Δ   0.25  1.94                                                                             1.03                                (Comparative Material)                                                                       Nonuniformity                                                                 like Gas Marks                                                 __________________________________________________________________________     Remarks: Criterion of Adhesivity                                              ⊚: No peeling                                                   ○ : Peeling occurrence at area of 50% or less                         Δ: Peeling occurrence at area of 20˜50%                      

In all of the samples on which surface sharp and minute unevennesseswere formed, the film and magnetic properties were improved, and afurther improvement in the watt loss was recognized in the samples whichwere further subjected to the strain-introduction by a knife.

EXAMPLE 10

A silicon steel-slab containing 0.073% of C, 3.20% of Si, 0.065% of Mn,0.030% of Al, 0.024% of S, 0.075% of Cu, 0.11% of Sn, and a balance ofiron was subjected, by a known method, to hot-rolling, annealing, andcold-rolling to obtain 0.225 mm thick sheets. The steel sheets werepolished, while varying the area percentage of the polished parts to60%, and 90%, by a brush roll, to form polished parts 3 μm in depth.Decarburization annealing was then carried out in an N₂ +H₂ humidatmosphere, and then, by using a marking-off needle, marking-off in adirection perpendicular to the rolling direction was carried out at adistance of 5 mm, so as to introduce the strain. Subsequently theapplication of an annealing separator, and finishing annealing werecarried out, and subsequently, the product sheets were obtained byheat-flattening after the application of an insulating coating. Theproperties of the films and the magnetic properties of the productsheets were measured, and the results were as shown in Table 11.

                                      TABLE 11                                    __________________________________________________________________________    Conditions                                                                             Marking-off                    Magnetic                              of Polishing                                                                           after  Properties of Glass Film                                                                              Properties                               after Cold-                                                                         Decarburi-     Adhesivity                                                                              Tension                                                                             B.sub.10                                                                         W.sub.17/50                        No.                                                                              Rolling                                                                             zation Appearance                                                                            (10 mmφ Bending)                                                                    (kg/mm.sup.2)                                                                       (T)                                                                              (W/kg)                             __________________________________________________________________________    1  3μ No     Uniform, thick                                                                        ⊚                                                                        0.52  1.92                                                                             0.88                                  60%          and excellent                                                 2  3μ Yes    Uniform, thick                                                                        ⊚                                                                        0.50  1.91                                                                             0.78                                  60%          and excellent                                                 3  3μ No     Uniform, thick                                                                        ⊚                                                                        0.58  1.92                                                                             0.85                                  90%          and excellent                                                 4  3μ Yes    Uniform, thick                                                                        ⊚                                                                        0.57  1.91                                                                             0.77                                  90%          and excellent                                                 5  No    No     Slightly thin,                                                                        Δ   0.28  1.94                                                                             0.93                               (Comparative Material)                                                                        Nonuniformity                                                                 like Gas Marks                                                __________________________________________________________________________

As in Example 9, the polished samples exhibited improved film propertiesand magnetic properties. In the samples which were further subjected tothe strain-introduction by a knife, a further improvement of the wattloss was obtained.

EXAMPLE 11

A silicon steel-slab containing 0.068% of C, 3.15% of Si, 0.070% of Mn,0.028% of Al, 0.025% of S, and a balance of iron was subjected, by aknown method, to hot-rolling, annealing, and cold-rolling to obtain 0.27mm thick sheets. The steel sheets were treated by a knife edge tointroduce 15 μm deep strains at a distance of from 5 mm to 20 mm and ina direction perpendicular to the rolling direction. The steel sheetswere then decarburization-annealed in an N₂ H₂ wet atmosphere, and thenactivation was carried out by polishing with sand paper to form 2.5 μmdeep polished parts over an area of 75%. Subsequently, the applicationof an annealing separator, and then finishing annealing at 1200° C. for20 hours, were carried out. The properties of the films and the magneticproperties were then measured, and the results were as shown in Table12.

                                      TABLE 12                                    __________________________________________________________________________    Strain-   Polishing                                                           Introducing                                                                             Treatment             Magnetic                                      Treatment after Properties of Glass Film                                                                      Properties                                       after Cold                                                                           Decarbur-                                                                           Adhesivity                                                                              Tension                                                                             B.sub.10                                                                         W.sub.17/50                                No.                                                                              Rolling                                                                              ization                                                                             (10 mmφ Bending)                                                                    (kg/mm.sup.2)                                                                       (T)                                                                              (W/kg)                                     __________________________________________________________________________    1  No     Yes   ⊚                                                                        0.58  1.95                                                                             0.91                                       2  Marking-off                                                                          Yes   ⊚                                                                        0.60  1.94                                                                             0.86                                          at a Distance                                                                 of 5 mm                                                                    3  Marking-off                                                                          Yes   ⊚                                                                        0.62  1.94                                                                             0.87                                          at a Distance                                                                 of 10 mm                                                                   4  Marking-off                                                                          Yes   ⊚                                                                        0.58  1.94                                                                             0.89                                          at a Distance                                                                 of 20 mm                                                                   5  No     No    Δ   0.28  1.95                                                                             0.97                                       (Comparative Material)                                                        __________________________________________________________________________

The decarburization-annealed and then polished samples exhibitedimproved adhesiveness, film-tension, and magnetic properties. In thesamples which were further subjected to strain-introduction bymarking-off, a further improvement of the watt loss was obtained.

EXAMPLE 12

A silicon steel-slab containing 0.076% of C, 3.20% of Si, 0.072% of Mn,0.026% of Al, 0.026% of S, and a balance of iron was subjected, by aknown method, to hot-rolling, annealing, and cold-rolling, therebyfinishing the slab to sheet thicknesses of 0.200 mm, 0.175 mm, 0.150 mm,and 0.125 mm. Samples were taken from the sheets having thesethicknesses and several were activated by sand paper having a grade of#100 to form sharp and minute unevennesses. The remaining sheets werenot activated. With regard to the activated and non-activated samples,the decarburization-annealing, application of annealing separator, andfinishing annealing were carried out. Further, the application of aninsulating coating and a measurement of the magnetic properties werethen carried out. Subsequently, after pickling, the macro-structure wasobserved. The results were as shown in Table 13.

                                      TABLE 13                                    __________________________________________________________________________    Polishing                                                                     Yes                     None                                                                    Ratio of          Ratio of                                        Magnetic                                                                             Watt Secondary                                                                           Magnetic                                                                             Watt Secondary                                 Sheet Flux Density                                                                         Loss Recrystal-                                                                          Flux Density                                                                         Loss Recrystal-                                Thickness                                                                           B.sub.10                                                                             W.sub.17/50                                                                        lization                                                                            B.sub.10                                                                             W.sub.17/50                                                                        lization                                  (mm)  (T)    (W/kg)                                                                             (%)   (T)    (W/kg)                                                                             (%)                                       __________________________________________________________________________    0.200 1.93   0.82 100   1.94   0.82 100                                       0.175 1.93   0.79 100   1.89   0.88 95                                        0.150 1.92   0.80 100   1.83   1.10 70                                        0.125 1.88   0.81 100   1.69   1.35 40                                        __________________________________________________________________________

EXAMPLE 13

A silicon steel-slab containing 0.060% of C, 3.30% of Si, 0.065% of Mn,0.030% of Al, 0.023% of S, 0.06% of Cu, 0.10% Sn, and a balance of ironwas subjected, by a known method, to hot-rolling, annealing, andcold-rolling, to obtain 0.30 mm thick sheets. These sheets aredesignated as "before treatment". The steel sheets were polished, bysand paper, while varying the roughness thereof, to form polished,uneven parts 10 μm, 6 μm, and 3 μm in terms of surface roughness, over a60% area of the steel sheets. Subsequently, decarburization-annealing ofthe sheets before treatment and of the polished sheets was carried outat 830° C. for 3 minutes in N₂ +H₂ gas, while varying the P H 0/P H to0.3, 0.4, 0.5, and 0.6. After the application of an annealing separator,the finishing annealing was carried out at 1200° C. for 20 hours.Subsequently, the product sheets were obtained by heat-flattening afterthe application of an insulating coating. The properties of the filmsand magnetic properties of the product sheets were measured, and theresults were as shown in Table 14.

                  TABLE 14                                                        ______________________________________                                                               Magnetic                                               Surface    Decarburization                                                                           Properties  Adhesivity                                 Roughness  Annealing   B.sub.10                                                                             W.sub.17/50                                                                          of film                                  (μm)    P.sub.H.sbsb.2.sub.O /P.sub.H.sbsb.2                                                      (T)    (W/kg) (%)                                      ______________________________________                                         1  3          0.3         1.94 1.13   30                                      2             0.4         1.93 0.95   3                                       3             0.5         1.93 0.93   0                                       4             0.6         1.94 0.93   0                                       5  6          0.3         1.93 1.20   25                                      6             0.4         1.92 0.93   0                                       7             0.5         1.93 0.90   0                                       8             0.6         1.92 0.91   0                                       9  10         0.3         1.91 1.18   25                                     10             0.4         1.92 0.93   0                                      11             0.5         1.91 0.88   0                                      12             0.6         1.91 0.90   0                                      13  0          0.3         1.94 1.09   70                                     14  (Comparative                                                                             0.4         1.93 1.04   65                                     15  Material)  0.5         1.93 1.03   65                                     16             0.6         1.93 1.03   60                                     ______________________________________                                         Remarks: Area Percentage of a film peeled by bending around 10 mmφ.  

We claim:
 1. A method of producing a grain oriented electrical steelsheet having an improved glass film adhesiveness and an improved wattloss, comprising the steps of:hot-rolling a silicon steel slab;annealing; cold-rolling once or twice or more, with an intermediateannealing therebetween; decarburization-annealing; applying an annealingseparator; and, finishing annealing wherein a glass film is formed onthe silicon steel sheet, the improvement comprising subjecting thecold-rolled steel sheet, prior to the decarburization annealing, to atreatment of a surface thereof to form sharp and minute unevennessesover an area of at least 50% of the steel sheet, wherein adjacent convexportions of said unevennesses are located at a depth of from 3 to 15 μmand at a distance of less than 1 mm from one another, and then thedecarburization annealing is carried out at a temperature of from 800°to 860° C. under a condition of PH₂ O/PH₂ ≧0.4, in which PH₂ O is apartial pressure of H₂ O in the decarburization annealing atmosphere,and PH₂ is a partial pressure of H₂ in the decarburization annealingatmosphere, and which forms an inner oxide layer partially protrudinginto the adjacent sharp convex portions of said unevennesses, applyingthe annealing separator, and finishing annealing, so that the glass filmis formed on said inner oxide layer.
 2. A method according to claim 1,wherein said surface treatment is carried out by a mechanical meanswhich is selected from the group consisting of brush rolling, buffpolishing, marking-off, sand papering, and grinding.
 3. A methodaccording to claim 1, wherein, after the surface treatment, and prior todecarburization annealing, pickling is carried out to attain a weightloss of 2.5 g/m² or more.
 4. A method according to claim 1 or 5, furthercomprising the step of imparting a strain to said steel sheet where saidunevennesses are formed, said strain imparting step occurring prior tosaid decarburization annealing step.
 5. A method according to claim 4,wherein said strain is imparted by one means selected from the groupconsisting of a laser, a marking-off, a knife, and a tooth form roll. 6.A method according to claim 1 or 5, wherein said sheet has a thicknessof from 0.23 mm or less.
 7. A method according to claim 1, furthercomprising the step of imparting a strain to said steel sheet where saidunevennesses are formed, said strain imparting step occurring after saiddecarburization annealing step and prior to said finishing annealingstep.
 8. A method for producing a grain-oriented electrical steel sheethaving an improved glass film adhesiveness and an improved watt loss,comprising the steps of:hot-rolling a silicon-steel slab, annealing,cold-rolling once or twice or more, with an intermediate annealingtherebetween, decarburization-annealing, applying an annealingseparator, and finishing annealing in which a glass film is formed onthe silicon steel sheet, the improvement comprising subjecting saidsteel sheet, subsequent to the decarburization annealing, to a treatmentof a surface thereof to form shaft and minute unevennesses, whereinadjacent convex portions of said unevennesses are located at a depth of3 to 15 μm and at a distance of less than 1 mm from one another, andwhich provide sites at which an inner oxide is partially protruded intothe silicon steel sheet during said finishing annealing.
 9. A methodaccording to claim 8, wherein said surface treatment is carried out by amechanical means which is selected from the group consisting of brushrolling, buff polishing, marking-off, sand papering, and grinding.
 10. Amethod according to claim 8, further comprising the step of imparting astrain to said steel sheet where said unevennesses are formed, saidstrain imparting step occurring after said decarburization annealingstep and prior to said finishing annealing step.